Surface characterization of a cross‐linked cytochrome c film on cysteamine‐modified gold electrodes

The aim of the present paper is to characterize a cross‐linked horse heart cytochrome c (HHC) film on cysteamine‐modified gold electrodes. The HHC film was deposited using 1‐ethyl‐3‐(3‐dimethylaminopropyl)‐carbodiimide (EDC) as a coupling agent. Attenuated total reflection infrared (ATR‐IR) spectroscopic analyses were performed to characterize the newly formed surface on a qualitative and conformational level. The film thickness was measured using a noncontact optical surface profiler, while quantitative data and information on the heterogeneity of the film were obtained by means of synchrotron radiation X‐ray micro fluorescence (SR micro‐XRF). Results indicate that, in addition to electrochemical studies, spectroscopic analysis methods are essential to gain insight in the effect of immobilization strategies on protein conformations. The latter is of relevance in the development and optimization of biosensors. Copyright © 2009 John Wiley & Sons, Ltd.     

Enantioselective route to 3-vinylidene tetrahydropyrans and 3-vinylidene oxepanes based on a silyl-Prins cyclization

A general method has been developed for the asymmetric synthesis of 3-vinylidene tetrahydropyrans and 3-vinylidene oxepanes based on the Lewis acid-catalyzed intramolecular reactions of oxocarbenium ions with propargylsilanes. The observed excellent diastereoselectivity and a high asymmetric induction offer a new synthetic method with a wide scope and generality.     

Identification of poliovirions and subviral particles by capillary electrophoresis

Poliovirions, purified from infected cell extracts with anion-exchange chromatography, can be analyzed and identified by CE in untreated fused silica capillaries using UV detection. Other subviral particles can be eluted as well from the same infected cell extract using a higher salt concentration buffer on the ion-exchange chromatography. Virions can be identified because of their conversion into empty capsids upon heating at 56°C. As a result of heating, the viral genome is released from the capsid. Here, we show that during this incubation some intermediate particles were found. The latter were identified by enzymatic peak shift analysis. The high salt concentration eluate subviral particles were analyzed with preincubation affinity CE together with their sensitivity for RNase and proteinase K treatment. Electropherograms of the higher salt concentration eluate display a mixture of at least four different subviral particles. One particle proved to have an [N1, H] antigenicity and was resistant to RNase and proteinase K digestion. The remaining particles were all sensitive to proteinase K treatment. This CE method proved to be valuable in the detection, identification and analysis of poliovirions and poliovirus particles offering an alternative powerful, cheap, fast and easy analysis method.     

On the collision and preimage security of MDC-4 in the ideal cipher model

We present a collision and preimage security analysis of MDC-4, a 24-years-old construction for transforming an n-bit block cipher into a 2n-bit hash function. We start with MDC-4 based on one single block cipher, and prove that any adversary with query access to the underlying block cipher requires at least \(2^{5n/8}\) queries (asymptotically) to find a collision. For the preimage resistance, we present a surprising negative result: for a target image with the same left and right half, a preimage for the full MDC-4 hash function can be found in \(2^n\) queries. Yet, restricted to target images with different left and right halves, we prove that at least \(2^{5n/4}\) queries (asymptotically) are required to find a preimage. Next, we consider MDC-4 based on two independent block ciphers, a model that is less general but closer to the original design, and prove that the collision bound of \(2^{5n/8}\) queries and the preimage bound of \(2^{5n/4}\) queries apply to the MDC-4 compression function and hash function design. With these results, we are the first to formally confirm that MDC-4 offers a higher level of provable security compared to MDC-2.     

Isospectral surfaces with distinct covering spectra via Cayley graphs

The covering spectrum is a geometric invariant of a Riemannian manifold, more generally of a metric space, that measures the size of its one-dimensional holes by isolating a portion of the length spectrum. In a previous paper we demonstrated that the covering spectrum is not a spectral invariant of a manifold in dimensions three and higher. In this article we give an example of two isospectral Cayley graphs that admit length space structures with distinct covering spectra. From this we deduce the existence of infinitely many pairs of Sunada-isospectral surfaces with unequal covering spectra.     

Path components of the space of gradient vector fields on the two-dimensional disc

We present a short proof that if two gradient maps on the two-dimensional disc have the same degree, then they are gradient homotopic.     

Regular partitions of dual polar spaces

We describe several classes of regular partitions of dual polar spaces and determine their associated parameters and eigenvalues. We also give some general methods for computing the eigenvalues of regular partitions of dual polar spaces.